DE2146636A1 - New indamine salts useful for dyeing keratin fibers, especially human hair - Google Patents

Description

PATEN TANW K LT E

PROF. DR. DR. J. REITSTÖTTER

DR.-ING. WOLFRAM BUNTE

DR. KARL GEORG LÖSCH

D - HOOO MÜNCHEN 13. BAUERSTRASSt it., FEF) NWUh lOnUl! / (ISil.l

2U6636

Munich, 1 7th SEP. 1971 M / 11656

L'OREAL
14, Rue Royale, Paris, France

New IndaminsäZize for dyeing keratin fibers, especially of human hair

The present invention relates to new indamine salts of the general formula (I)

R-

N -

R /

M-)

209813/1746

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wherein R ₁ and R ₂ »which can be the same or different, a lower alkyl radical (with 1 to 4 carbon atoms), R, and R ^, which can be the same or different, a lower alkyl radical, which may optionally be with a hydroxyl, amino or Acylamino radical can be substituted. Rc and Rg, which can be the same or different, represent a hydrogen atom or a lower alkyl or lower alkoxy radical and R an amino, acylamino or hydroxyl radical, η an integer equal to 1 or 2 and y? ~ ^ ~ ' An anion such as Persulfate, perchlorate, chloride, bromide anion or ZnCl, "denotes, the compounds according to the invention also being able to exist in a tautomeric form of the formula (I).

The indamine salts of the formula (I) can be obtained by condensation of a p-phenylenediamine of the formula (II)

wherein R, and R ^ have the meanings given above, with a compound of the formula (III)

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in which R ₁ , R ₂ , Rc, Rg and R have the meanings given above, in an aqueous, aqueous alcoholic or aqueous acetonij shem alkaline medium in the presence of an oxidizing agent such as hydrogen peroxide or an alkali metal persulfate, where the compounds (II) and (III ) can be used in the form of one of their salts, and then add to the reaction mixture a salt of the acid corresponding to the desired indamine salt, which acid is more water-soluble than this indamine salt, in order to precipitate the latter from the reaction mixture. '

The salt added can, for example, be an alkali persulfate, ammonium persulfate, an alkali perchlorate, an alkali chloride or bromide, or zinc chloride, in which case a zinc double salt is obtained.

If an alkali persulphate or ammonium persulphate is used as the oxidizing agent, it is often the case that is not very water-soluble Indamine persulfate as soon as condensation takes place. It has been found, however, that it is often preferable to work in two stages if one wants to obtain the indamine persulphates with a greater degree of purity by first the condensation is carried out with the aid of hydrogen peroxide and then ammonium persulphate is added.

The p-phenylenediamines of the formula (II) used in the implementation of the process according to the invention can be used, for example: Ν, Ν-diethyl-p-phenylenediamine, Ν, Ν-dimethyl-p-phenylenediamine, N, N- (ethyl-ß-piperidinoethyl) -p-phenylenediamine, N, N- (ethyl-ß-acetamino-ethyl) -p-phenylenediamine, N, N- (di-ß-hydroxyethyl) -p-phenylenediamine.

The compounds of the formula (III) which are used in carrying out of the method according to the invention can be used, for example: m-diethylaminophenol, N, N-dimethyl-m-phenylenediamine, m-N, N- (diethyl) -aminoacetanilide.

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You can also use the indamine salts of the formula (I) Condensation of a compound of the formula (III) with a nitroso derivative of the formula (IV)

in which fU and R ^ have the meanings given above, either in an aqueous medium or in an ethanolic medium and in the presence of zinc chloride.

When conducting this condensation in aqueous medium, is preferably used the nitroso derivative (IV) in the form of the hydrochloride or hydrobromide, and operates at a temperature between 30 and 60 ⁰ C. It is then isolated a Indaminchlorid or bromide of formula (I) by filtration , if necessary after salting out. · ■

If the above condensation is carried out in an ethanol medium, the nitroso derivative of the formula (IVO which has not been converted into a salt) is used and reflux is used in the presence of zinc chloride, a double chloride of zinc and the indamine of the formula (I) is then isolated.

The nitroso derivatives of the formula (IV) which are used in carrying out the second process according to the invention can include, for example: p-nitroso-N, N-diethylaniline, p-Nitroso-N, N-dimethylaniline, p-Nitroso-N, N- (ethyl-ß-acetyl-r aminoethyl) aniline, p-nitroso-N, N- (di-ß-hydroxyethyl) aniline

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Μ / ιιβ56. '2H6636

and p-nitroso-N, N- (ethyl-ß-piperidinoethyl) aniline.

The indamine salts according to the invention are dyes which can be used in a broad pH range, from pH 3 to pH 10 is enough to have a great coloring power. Due to their very high affinity for keratin fibers, very, low ones are sufficient Concentrations of these dyes to obtain intense nuances, which also explains why these salts are flawless can be used, although they are relatively insoluble in water.

Accordingly, the present invention also relates to a new coloring agent for keratin fibers, particularly for human ones Hair which is characterized in that it contains at least one compound of the formula (I ·) in solution.

The colorants according to the invention can only contain compounds of formula (i), in which case one can achieve colorations on white hair that go from blue to green, and this after an extremely short exposure time of the order of 3 minutes at ambient temperature.

Due to the great coloring power of the new compounds of the formula (I), their concentration in the inventive Agents, as mentioned above, can be extremely low, on the order of 0.002% by weight. However, this concentration can

0.002 parts by weight 96 to 1 wt -.% vary. ^}

The agents according to the invention can contain other direct dyes, for example anthraquinone dyes, nitro dyes Benzene series, indoanilines, indophenols or other indamines than those of the formula (I) contain.

The agents according to the invention can be used to obtain reflective nuances which often give the hair a pearly appearance.

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The colorants according to the invention are generally in Form of aqueous or aqueous-alcoholic solutions, which can easily be dissolved in one or more water Compounds of the formula (i), if appropriate as a mixture, with other direct dyes. However, they can also contain thickeners and in the form . of creams or gels are available .. ',

The agents according to the invention can also contain various constituents commonly used in cosmetics, for example wetting agents, dispersants, swelling agents, penetrants, emollients ¹ or perfumes. They can also be conditioned in aerosol bottles.

The pH of the colorants according to the invention can vary between and 10, but is preferably between 4 and 9.

The dyeing of keratin fibers, especially human ones Hair, with HiXe of the coloring agent according to the invention is carried out in the usual way by applying the agent to the to be colored Fibers left in contact with for a time varying between 3 and 30 minutes, followed by rinsing and optionally washing and drying the fibers.

The dyes according to the invention can also be in the form of

Hair lotions can be used.

The present invention therefore also provides a 'new agent, which is characterized in that it is in aqueous-alcoholic solution contains at least one cosmetic resin and at least one compound of the formula - (I).

The proportion of the compounds of the formula (I) in the water wave lotions according to the invention can be extremely low.

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This proportion generally varies from 0.002 to 0.5% by weight.

The cosmetic resins that can be included in the water wave lotions of the invention include: Polyvinylpyrrolidone, crotonic acid-vinyl acetate copolymers, Vinyl pyrrolidone / vinyl acetate copolymers, maleic anhydride / butyl vinyl ether copolymers, etc. These resins are used in an amount of 1 to 3% by weight.

The alcohols suitable for producing the water-waving lotions according to the invention are the alcohols with a low molecular weight, preferably ethanol or isopropanol. These alcohols are used in a proportion of 20 to 50% by weight. -% used.

The pH of the water wave lotion according to the invention can vary between 3 and 10, but is preferably between

6 and 8.!

The water wave lotions according to the invention, which only contain dyes of the formula (i) according to the invention, provide nuanced Means that give the hair extraordinarily luminous reflections and often a pearly or iridescent appearance can lend.

The water wave lotions according to the invention can also be others Direct dyes, for example anthraquinone dyes, nitro dyes of the benzene series, indoanilines, ind'ophenols or also contain other indamines.

The water waves according to the invention are applied in the usual way to damp hair, which has been done beforehand washed and rinsed, followed by curling and drying of the hair.

209813 / me

M / 11656 £ 2 UB 6

The following examples are intended to further illustrate the invention, but not to limit it. The temperatures are measured ^{in 0 C.}

example

Production of N- [4- (ethyl-ß-piperidino-ethyl) -amino-phenyl] · 3-hydroxy-benzoquinone imine-N ', N'-diethyliminium zinc double ■ chloride of the formula

3.1 g (0.012 mol) of p-nitroso-N, N- (ethyl-ß-piperidinoethyl) aniline are dissolved and 1.9 g (0.012 mol) of m-diethylaminophenol in 20 cnr absolute ethanol. 1.7 g are added to this solution Zinc chloride and reflux the reaction mixture for 30 minutes. After cooling, it is suctioned off, washed with ethanol, dries in vacuo and receives 4.80 g of the double salt of zinc and the expected indamine. The product is chromatographic pure.

209813/1746

Example 2

Production of N- [4- (ethyl-acetylamino-ethyl) -amino-phenyl] ■ 3-acetylamino-benzoquinoneimine-N ¹ , JM'-cLimethyliminium-zinc

double chloride of the formula

MOOCH-,

WIIöOCH-5 ■ '

CII

To a solution of 2.35 g (0.01 mol) of p-nitroso-N, N- (äthylacetylaminoäthyl) aniline 1.78 g (0.01 mol) of 3-dimethylamino-acetanilide in 10 cnr of absolute ethanol are added to 10 cnr * absolute ethanol and 2 g zinc chloride. The reaction mixture is refluxed for 30 minutes and then cooled and sucks off 2 g of the double salt of zinc and the indamine. This Doppelsalζ is chromatographic after washing with ethanol pure.

Example 3

Preparation of N - [(4-dimethylamino) phenyl] -3-hydroxybenzoquinone imine-N ¹ , N ¹ -diethyliminium zinc double chloride of the formula

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3 g (0.02 mol) of p-nitroso-dimethylaniline and 3.3 g are dissolved (0.02 mol) m-dietary laminopheno 1 in 20 cm ^ absolute ethanol. 3.3 g of zinc chloride are added to this solution and the reaction mixture is refluxed for 30 minutes. After cooling down It is filtered off with suction, washed with ethanol and dried in vacuo and 4.75 g of the double salt of zinc and indamine are obtained. This The product is chromatographically pure.

Example 4

Production of N- [4- (ethyl-ß-acetylamino-ethyl) -amino-phenyl] -3-hydroxy-benzoquinonimine-N ', N'-diethyliminium zinc double chloride

ZnCl ₃ "

^ h- / Vn =

OH ₂ - (Jh ₂ -MHCOCEL

4.7 g (0.02 mol) of p-nitroso-N, N- (ethyl-ß-acetylaminoethyl) aniline are dissolved and 3.3 g (0.02 mol) of m-diethylaminophenol in

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30 cm of absolute ethanol. 3 g of zinc chloride are added to this solution and reflux the reaction mixture for 30 minutes. After cooling, it is filtered off with suction and washed with ethanol and dries and receives 8.4 g of double chloride of zinc and the expected indamine. This product is chromatographically pure.

Example 5

Preparation of N - [(4-Dimethylamino) phenyl] -3-acetylaminobenzoquinone imine-N ^T , N'-dimethyliminium chloride

HICOCH./ 5

37.3 g (0.2 mol) of p-nitroso-NjN-dimethylaniline hydrochloride are dissolved in 380 cnr of water at 50 °. 35.6 g (0.2 mol) of mN, N-dimethylaminoacetanilide in 400 cm ^{3 of} water at 50 ° are quickly added to this solution with stirring. Maintaining the reaction, mixture for 2 hours at 50 ⁰ C. Then, to 20 g of sodium chloride were added. After cooling to 5 ° for 4 hours, the product is filtered off with suction, washed with a little water and then with acetone and 53 g of the expected imine chloride are obtained, crystallized in the form of monohydrate. This product is chromatographically pure.

Analysis C ₁₈ H ₂ ^ N

C H 'N

calculated: 59.25 6.85 15.30

found: 59.00 6.75 15.10

58.92 6.78 x 15.07

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Example 6

Preparation of N - [(4-dimethylamino) phenyl] -3-amino- "benzoquinoneimine-N ', N'-dimethyliminium perchlorate

ClO ~

Dissolve 2.09 g (0.01 mol) of N, N-dimethyl-p-phenylenediamine dihydrochloride and 1 g (0.05 mol) of N, N-dimethyl-m-phenylenediamine dihydrochloride in 20 cnr water, which is 5 cnr 22 ⁰ B are added to ammonia. 20 cnr hydrogen peroxide in 20 volumes are immediately added to the mixture. It takes on an intense blue color. After 10 minutes at ambient temperature, 10 g of sodium perchlorate are gradually added with stirring. The expected Indaminperchlorat \ precipitated in the form of vongranatroten crystals having the chromatogram as a contaminant traces of N, N-dimethyl-p-phenylenediamine. After washing with ethyl acetate, the perchlorate is chromatographically pure.

Analysis Z- g ^ J & ifiiS " ^

C. 10 . H 69 N 19th calculated: 52, 21st 5, 74 15, 24 found: 52, 97 5, 72 • 15, 16 51, 5, 15,

-IZ-

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Example 7 ■ '

Preparation of N - [(4-Dimethylamino) phenyl] -3-acetylaminobenzoquinone imine-N ', N'-dimethyliminium persulfate.

Dissolve 1.05 g (0.05 mol) of N, ^ dimethyl-p-phenylenediamine dihydrochloride in 10 cm of water to which 0.8 cnr ammonia and 0.89 g (0.05 mol) of dimethylamino-in.- acetanilide car in 5 of water, which is mixed with 5 cnr acetone.

The two solutions are mixed, cooled to 0 ° and 1.19 g (0.05 mol) of ammonium persulfate in 10 cm of water are added with stirring to. After 10 minutes "the expected indamine persulfate" is sucked off in the form of green crystals with golden reflections, which are chromatographed after washing with a little ice water is pure.

Example 8

The following solution is created:

Dye according to Example 1 '0.15 g

Crotonic acid / vinyl acetate copolymer 2 g

(90 % vinyl acetate, 10 % crotonic acid, molecular weight 45,000 to 50,000).

Alcohol at 96 ° as much as required. me for 50 °

Water as much as * required for 100 g

Triethanolamine as much as required for pH 7

If this solution is applied to bleached hair as a water wave lotion, it gives it a forget-me-not blue Nuance with a mother-of-pearl shimmer.

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Example 9

The following solution is created:

Dye according to Example 3 0.1 g

Crotonic acid / vinyl acetate mixed polymer 2 g (90 % vinyl acetate, 10 % crotonic acid,
Molecular weight 45,000 to 50,000)

Alcohol at 96 ° as much as necessary for 50 °

Water as much as necessary for 100 g Triethanolamine as much as required for pH 7

If this solution is applied as a water wave lotion, it is decolorized On hair, it gives it an intense, very luminous turquoise blue shade.

Example 10

The following solution is created:

Dye according to Example 1 · 0.002 g

Water as much as needed for. 100 g

Ammonia with 22 ⁰ B as much as necessary for pH 10

Bring this solution to decolorized for 10 minutes
Hair on, so it results after rinsing and shampooing
a silver-blue shade.

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D. υ i s ρ i e 1 11

The following solution is created:

Dye according to Example 4 0.1 g

Crotonic acid / vinyl acotate copolymer 2 g

(90: "i vinyl acetate, 10 ⁽ / o crotonic acid,; -: uloiiularj-weight 45,000 to 50,000) alcohol rai ο 96 ° as much v / ie necessary for 50 ° V. Water as much v / ie necessary for 100 g triethanolaiain as much as necessary for pH 7

. ■ one wrestles the- '.' ^ Nv ^ g as water weliotion on discolored iluars, γ · .-. .. ... “Ie this one a light blue shade with a strong Porlmutt shimmer.

B e i s ώ i e 1 12

The following solution is created:

Dye according to Example 5 0.2 g

','. 'ater as much as necessary for' 100 g

The pH of the solution is 6.5

Bring this solution up to 95 ^ for 10 minutes, of course On white hair, it gives a very 'censive, green shade' after rinsing and shampooing.

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BATH

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Example 13

The following solution is produced

Dye according to Example 3 '. '', 0.2 g Alcohol with 96 ° * 25 g

Water as much as necessary for 100 g

10% lactic acid solution as much as required for pH 3.3 '

Apply this solution for 20 minutes. Of course, 95% W white hair, so it gives a bright emerald green shade after rinsing and shampooing. »

Example 14

The following solution is found:

Dye according to Example 2 .. 0.15 g

/ Crotonic acid / vinyl acetate copolymer 2 g

(90% vinyl acetate, 10% crotonic acid, molecular weight 45,000 to 50,000)

Alkenol nio 96 ° as much as necessary for 50 °

P V.'ascer as much v / ie required for 100, g

Triächanolairiin as much as necessary for pH 7

Rr.sn brings this solution to decolorized as a water wave lotion Hair, it gives it a light green shade with gold reflections.

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209813/1746 ₈ ad original

Example Ir? . . .

You create the following solution: '■' "

Dye according to Example 1. 0.05 g

N - [(2 ¹ , 4'-diamino-5'-methoxy) -. Phenyl] -

benzoquinone imine 0.05 g

Alcohol mix 96 ° - 25 g,

Water as much as necessary for 100 g

Ammonia with 22 ⁰ B as much as required 'for pH 10

If you apply this solution to 95 % natural white hair for 10 minutes, it gives it a dark beige-violet shade. *. - ·

Example 16

The following solution is created:

Dyestuff according to Example 3 0.25 g

Nitro-p-phenylenediamine 0.5 g

Alcohol with 9 (3 ° 25 g

Water as much v / ie required for 100 g

Ammonia with 22 ⁰ B as much as required for pH 10.5

If you apply this solution for 10 minutes to 95 % naturally white ο laare, it gives this after rinsing and shar: * poü / iieren an intense yellow-green nuance »

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/ 9 2U6636

B 3 i ε Ό i e I 2.7

The following solution is created:

Dye according to Example 5 0.2 g

Xrotonic acid / vinyl acetate copolymer "2 g (90> ό vinyl acetate., 10> o! Crotonic acid,. ^ O leiiular weight 45 OGO to 50,000) ■■. ■""alcohol .v.it. 90 ° - so much -as necessary-for 50 ^u ■ ^: 'Trietlianolarain as much -v / ie required -for - - ■■ - pK 7 water as much v / ie required for IOC g

Bringing this solution as Wasserwellotion .on 'hellbraur ^ s hair, it gives ^one this-a dark brown shade with green highlights. ·

on SOi el 18

Kan makes the following solution;

Dye according to Example 4 0.3 g

Buty! Glycol 5 g of lauryl alcohol, oxyethylene with

10.5 moles of ethylene oxide 5 ' S

Masser coviel v / ie required for 100 g

If you apply this solution to 60 % natural white hair for 20 minutes, it gives it a green-gray shade after rinsing and shading.

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209813/1746 ßAD ORIGINAL

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Example 19

The following solution is created:

Dyestuff according to Example 6 0.05 g

Alcohol with 96 ° * 25 g

Water as much as necessary for 100 g

Bringing this solution, the pH is 8 to 95% naturally white hair on, we get to rinse and shampoo! Ng a blue-green shade with silver shimmer.

Example 20

The following solution is created:

Dyestuff according to Example 7 0.1 g

Crotonic acid / vinyl acetate copolymer 2 g

(90 % vinyl acetate, 10 % ! Crotonic acid, molecular weight 45,000 to 50,000) alcohol with 96 ° as much as necessary for 50 °

Water as much as necessary for 100 g

Triethanolamine as much as required for pH 7

If you apply this solution to bleached hair as a water wave lotion, it gives it a light jade green shade.

The terms "lower alkyl" and "lower alkoxy" used in describing the present invention denote in each case aliphatic radicals with 1 to 4 carbon atoms. Also used in describing the present invention The term "acyl" (in acylamino) denotes aliphatic acyl radicals which also contain 1 to 4 carbon atoms.

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2098 13/1746 8AO ORiQ _[NAL

Claims (24)

I «godfather, η t a η a ρ r ü'e h e 1 .. New indamine salts of the general formula (I) ₄ ■ R, M-) where R ^ and Rp, dLe can be the same or different, denote a lower alkyl radical, H ^ land R ^, which can be identical or different, denote a lower alkyl radical which is optionally substituted by an amino, hydroxyl or acylamino radical, R, - and Rg, which can be the same or different, represent a hydrogen atom or a lower alkyl or lower alkoxy radical and R an amino, acylamino or hydroxyl radical, η is an integer equal to 1 or 2, and χ ^η ^ "" · 'a Anion "means, including the tautomeric forms of these compounds of the formula (I). 2. Process for the preparation of the indamine salts according to Claim 1, characterized in that a p-phenylenediamine of the formula (II) - 20 - 209813/1746 ORIGINAL INSPECTED M / 11656 wherein FU and R ^ have the meanings given in claim 1 possess, with a compound of the formula (III) N ' ^X 5 where R and R those given in claim 1 Have meanings in aqueous, aqueous alcoholic or aqueous acetone alkaline medium ^ in the presence of a Oxidizing agent condensed, wherein the compounds (II) and (Hl) can be used in the form of one of their salts, and then to the reaction mixture a salt of the acid corresponding to the desired indamine salt which is more water soluble than this indamine salt. 3. The method according to claim 2, characterized in that the oxidizing agent used is an inorganic one J is persalt and that the indamine salt formed is filtered off is isolated. - 21 2Q9813 / 1746 ORJfcJNAL INSPECTED 214S636 4. The method according to claim 3, characterized in that. that the inorganic persalt is an alkali persulfate or Is ammonium persulfate. O. Method ge: iä.3 claim 2, characterized in that the oxidizing agent used is hydrogen peroxide. ₍ 6. Process for the preparation of the indaminsaize according to Claim 1, characterized in that a compound of formula III, as defined in claim 2, with a Xitroso derivative of the formula (IV) ^R 4 wherein R ₇ and R ^ have the meanings given in claim 1, condensed either in an aqueous medium or in an ethanol medium and in the presence of zinc chloride, it being possible to use the nitroso derivative of the formula IV in the form of the hydrochloride or hydrobromide. ' 7. The method according to claim 6, characterized in \ that the condensation in an aqueous medium at a Temperature between 30 and. 60 ⁰ C and the nitroso! derivative of the formula IV used in the form of hydrochloride or hydro-bromide. -.22 2098 ORIGINAL M / 11656 8. The method according to claim 6, characterized in that that the condensation is carried out in an ethanolic medium and in the presence of zinc chloride and that used Nitroso derivative of the formula (IV) not in the form of a salt is present. 9. Colorants for keratin fibers, especially for Human hair, characterized in that it contains at least 1 indamine salt in an aqueous or aqueous-alcoholic solution according to claim 1 contains. 10. Composition according to claim 9, characterized in that its pH is between 3 and 10. 11. Composition according to claim 10, characterized in that its pH is between 4 and 9 .. 12. The composition of claim 9, characterized in that 0.002 to 1 wt -% contains Indaminsalz.. 13. Composition according to claim 9, characterized in that it contains other direct dyes for hair. 14. Composition according to claim 9, characterized in that there are wetting agents, dispersants, penetrants, Contains thickeners or any other ingredient commonly used in hair cosmetics. - 23 209813/1746 M / 11656 15- Method of dyeing keratin fibers, in particular of human hair, characterized in that the fibers to be colored with an agent according to one of the Claims 9 "to 14 soaks and after a time that is 3 Ms 30 minutes, the fibers rinsed and, if necessary, shampooed and dried. 16. Dyed water wave lotion for keratin fibers, especially for human hair, characterized in that it is in aqueous-alcoholic solution at least one cosmetic "Resin and at least one indamine salt according to claim 1 contains. 17. Means according to claim 16, characterized in that it contains 0.002 to 0.5 wt% indamine salt. 18. Composition according to claim 16, characterized in that the alcohol it contains is a low alcohol Molecular weight is. k 19. Agent according to claim 18, characterized in that the alcohol is ethanol or isopropanol. 20. Agent according to claim 16, characterized in that it contains 20 to 50% by weight of alcohol. - 24 - 209813/1746 Ι Μ / 11656 & 2U6636 21. Means according to claim 16, characterized in that the cosmetic resin which it contains is polyvinylpyrrolidone, or a crotonic acid / vinyl acetate copolymer, Vinyl pyrrolidone / vinyl acetate copolymer or maleic! acid anhydride / butyl vinyl ether copolymer. 22. Agent according to claim 16, characterized in that it contains 1 to 3% by weight of cosmetic resin. 23. 'Agent according to claim 16 to 22, characterized in that it has a pH between 3 and 10 « 24. Composition according to claim 23, characterized in that it has a pH between 6 and 8 _e - 25 209813/1746 ORIGINAL INSPECTED